KR102025997B1 - New materials with aza-dibenzothiophene or aza-dibenzofuran core for pholed - Google Patents

Abstract

A new class of compounds is provided that contain aza-dibenzothiophene or aza-dibenzofuran. The compounds can be used in organic light emitting devices that provide improved stability, improved efficiency, long life and low operating voltages. In particular, the compound may be used as a host material of a light emitting layer having a host and a light emitting dopant or as a material in a reinforcing layer.

Description

NEW MATERIALS WITH AZA-DIBENZOTHIOPHENE OR AZA-DIBENZOFURAN CORE FOR PHOLED}

This application claims priority to US Provisional Application No. 61 / 145,370, filed January 16, 2009, the disclosure of which is incorporated herein by reference in its entirety. This application is related to US Provisional Application No. 12 / 209,928, filed September 12, 2008, and US Provisional Application No. 11 / 443,586, filed May 31, 2006.

The claimed invention was formed by, and on behalf of and / or in connection with, one or more of the following sections of the United Academic Research Agreement: Regency of the University of Michigan, Princeton University, the University of Southern California and Universal Display Corporation. The consultations took place before and when the claimed invention was formed, and the claimed invention was formed as a result of activities carried out within the scope of the agreement.

Technical field

The present invention relates to novel organic complexes containing aza-dibenzothiophene or aza-dibenzofuran. The material may be useful for organic light emitting diodes (OLEDs).

Optoelectronic devices using organic materials are becoming more preferred for many reasons. Many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices can be cost advantageous over inorganic devices. In addition, the inherent properties of the organic material, such as its flexibility, may make the material suitable for certain applications, such as manufacturing on flexible substrates. Examples of organic optoelectronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. In OLEDs, organic materials may have performance advantages over conventional materials. For example, the wavelength emitted by the organic light emitting layer can generally be easily changed by an appropriate dopant.

OLEDs use thin organic films that emit light when voltage is applied across the device. OLEDs are becoming a more interesting technology for use in applications such as flat panel displays, lighting and backlighting. Several OLED materials and arrangements are described in US Pat. Nos. 5,844,363, 6,303,238 and 5,707,745, which are incorporated herein by reference in their entirety.

One use for phosphorescent light emitting molecules is full color displays. Industrial specifications for such displays require pixels adapted to emit a particular color, referred to as the 'saturation' color. In particular, the standard requires saturated red, green and blue pixels. Color can be measured using 1931 CIE coordinates known in the art.

One example of a green luminescent molecule is tris (2-phenylpyridine) iridium, which means Ir (ppy) ₃ having the structure:

In the present and subsequent figures herein, the inventors show coordination bonds from nitrogen to metal (here Ir) as straight chain.

As used herein, the term 'organic' includes polymeric materials as well as small molecule organic materials that can be used to make organic optoelectronic devices. 'Small molecule' means any organic material that is not a polymer, and 'small molecules' may be substantially quite large. Small molecules may include repeat units in some circumstances. For example, using long chain alkyl groups as substituents does not remove molecules from this 'small molecule' class. Small molecules may also be included in the polymer, for example as pendant groups on the polymer backbone or as part of its backbone. Small molecules can also serve as the central portion of a dendrimer, which consists of a series of chemical shells formed on the central portion. The central portion of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be 'small molecules', and all dendrimers currently used in the OLED field are thought to be small molecules.

As used herein, 'top' means the furthest from the substrate, while 'bottom' means the closest to the substrate. If the first layer is described as 'disposed on' the second layer, the first layer is disposed farther from the substrate. Other layers may be present between the first and second layers unless the first layer is specified as 'in contact with the second layer'. For example, various organic layers may be present between, but the cathode may be described as being 'placed on' the anode.

As used herein, 'solution processable' means that it can be transported, dispersed or dissolved in and / or from a liquid medium in the form of a solution or suspension.

A ligand is referred to as 'photoactive' when the ligand is considered to directly contribute to the photoactive properties of the luminescent material. Although the auxiliary ligand may alter the properties of the photoactive ligand, if the ligand does not contribute to the photoactive properties of the luminescent material, the ligand may be referred to as 'secondary'.

As used herein, and as generally understood by one of ordinary skill in the art, if the first energy level is closer to the vacuum energy level, the first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" "(LUMO) energy level is greater than" or "higher" than the second HOMO or LUMO energy level. Since ionization potential (IP) is measured as negative energy relative to vacuum level, higher HOMO energy levels correspond to IPs with smaller absolute values (smaller negative IPs). Similarly, higher LUMO energy levels correspond to electron affinity (EA) with lower absolute values (EA with lower negative values). In a conventional energy level diagram where the vacuum level is at the top, the LUMO energy level of the material is higher than the HOMO energy level of the same material. The "higher" HOMO or LUMO energy levels appear closer to the top of such diagrams than the "lower" HOMO or LUMO energy levels.

As used herein and as will be generally understood by those skilled in the art, the first work function is 'greater' or 'higher' for the second work function when the first work function has a higher absolute value. Since the work function is usually specified as a negative number for the vacuum level, it means that the 'higher' work function is more negative. At typical energy levels where the vacuum level is at the top, a 'higher' work function is illustrated farther downward from the vacuum level. Thus, the definitions of HOMO and LUMO energy levels follow different conventions than work functions.

Further details about OLEDs, and the foregoing definitions, can be found in US Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

(X₁ 및 X₂ 중 하나는 질소이고, X₁ 및 X₂ 중 다른 하나는 탄소이며, Y는 S 또는 O임)을 갖는 아미노-아릴티오 피리딘 중간체의 아세트산 용액을 ^tBuONO로 처리하여 화학식

을 갖는 아자 착물을 생성하는 것을 포함한다. R₁ 및 R₂는 1개, 2개, 3개 또는 4개의 치환을 나타낼 수 있다. R₁은 수소, 알킬, 아릴, 헤테로아릴 및 할라이드로 구성된 군으로부터 선택된다. 바람직하게는, R₁은 할라이드이다. R₂는 수소, 알킬, 아릴 및 할라이드로 구성된 군으로부터 선택된다. 바람직하게는, X₁ 및 X₂ 중 하나는 탄소일 수 있고, 다른 하나는 질소일 수 있다. 더욱 바람직하게는, X₁이 질소이고 X₂가 탄소이거나, X₁이 탄소이고 X₂가 질소이다. 바람직하게는, Y는 S이다. 대안적으로, Y는 바람직하게는 O일 수 있다. R₂는 1 이상의 할라이드를 포함할 수 있고, R₂는 할라이드 치환기만을 포함할 수 있다. 상기 방법을 이용하여 R₂가 할라이드가 아닌 화합물을 제조할 수 있고, 상기 아미노-아릴티오 피리딘 중간체는 ^tBuONO에 의한 처리 전에 H₂SO₄로 처리한다.

의 수율은 50% 이상일 수 있다.A method for producing an aza-dibenzothiophene compound or an aza-dibenzofuran compound is provided. The method is formula

An acetic acid solution of an amino-arylthio pyridine intermediate having (one of X ₁ and X ₂ is nitrogen, the other of X ₁ and X ₂ is carbon and Y is S or O) is treated with ^t BuONO

Generating an aza complex having: R ₁ and R ₂ may represent 1, 2, 3 or 4 substitutions. R ₁ is selected from the group consisting of hydrogen, alkyl, aryl, heteroaryl and halide. Preferably, R ₁ is a halide. R ₂ is selected from the group consisting of hydrogen, alkyl, aryl and halides. Preferably, one of X ₁ and X ₂ may be carbon and the other may be nitrogen. More preferably, X ₁ is nitrogen and X ₂ is carbon, X ₁ is carbon and X ₂ is nitrogen. Preferably, Y is S. Alternatively, Y may be preferably O. R ₂ may include one or more halides and R ₂ may include only halide substituents. The method can be used to prepare compounds in which R ₂ is not a halide, and the amino-arylthio pyridine intermediate is treated with H ₂ SO ₄ before treatment with ^t BuONO.

The yield of may be at least 50%.

Novel classes of aza-dibenzothiophene and aza-dibenzofuran compounds are provided. The compound has the formula

화학식 (I)

Formula (I)

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are independently selected from the group consisting of carbon and nitrogen atoms, and X ₁ , X ₂ , X ₃ , X ₄ , X _{At least one of 5} , X ₆ , X ₇ and X ₈ is a nitrogen atom. Y is S or O. R ₁ and R ₂ may represent 1, 2, 3 or 4 substitutions. R ₁ and R ₂ are independently selected from the group consisting of hydrogen, alkyl, aryl and halides, and at least one of R ₁ and R ₂ is selected from the group consisting of:

R ' ₁ , R' ₂ , R ' ₃ and R' ₄ can represent one, two, three, four or five substitutions and R ' ₁ , R' ₂ , R ' ₃ and R' ₄ is independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. Preferably, m and n are 0, 1, 2, 3 or 4; m + n is 2 or more and m + n is 6 or less. Preferably, R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently hydrogen or methyl.

Alternatively, novel classes of aza-dibenzothiophene and aza-dibenzofuran compounds are provided. The compound has the formula

화학식 (I)

Formula (I)

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are independently selected from the group consisting of carbon and nitrogen atoms, and X ₁ , X ₂ , X ₃ , X ₄ , X _{At least one of 5} , X ₆ , X ₇ and X ₈ is a nitrogen atom. Y is S or O. R ₁ and R ₂ may represent 1, 2, 3 or 4 substitutions. R ₁ and R ₂ are independently selected from the group consisting of hydrogen, alkyl, aryl and halides, and at least one of R ₁ and R ₂ is selected from the group consisting of:

R ' ₃ and R' ₄ may represent one, two, three, four or five substitutions, and R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently hydrogen, alkyl, Heteroalkyl, aryl and heteroaryl. Preferably, m and n are 0, 1, 2, 3 or 4; m + n is 2 or more and m + n is 6 or less. Preferably, R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently hydrogen or methyl.

One of R ₁ and R ₂ is hydrogen, the compound is selected from the group consisting of R ₁ and R the other of the _two is also provided:

or

Also provided are compounds in which both R ₁ and R ₂ are selected from the group provided herein. Moreover, compounds are provided wherein R ₁ is selected from the group provided herein.

Specific examples of aza-dibenzothiophene compounds and aza-dibenzofuran including compounds 1 to 93 are provided.

Aza-dibenzothiophene compounds and aza-dibenzofuran compounds comprising compounds 1 to 79 are provided.

A first device is provided that includes an organic light emitting device. The device also includes an anode, a cathode, and an organic layer located between the anode and the cathode. The organic layer comprises a compound having formula (I). In particular, the organic layer of the device may comprise a compound selected from compounds 1 to 93.

In one aspect, the first device is a consumer product.

An organic light emitting device is also provided. The device includes an anode, a cathode, and an organic layer located between the anode and the cathode. The organic layer comprises a compound having formula (I). In particular, the organic layer of the device may comprise a compound selected from compounds 1-79. Preferably, the organic layer is a light emitting layer and the compound having formula (I) is a host. The light emitting layer may further include a light emitting dopant. Preferably, the luminescent dopant has the formula:

, 여기서, R₁ 및 R₂는 각각 독립적으로 수소, 알킬 및 아릴로 구성된 군으로부터 선택된다.

, Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, alkyl and aryl.

In addition, consumer products are also provided. The product contains an anode, a cathode, and an organic layer between the anode and the cathode, the organic layer comprising a compound of formula (I).

1 shows an organic light emitting device.
2 shows an inverted organic light emitting device without an individual electron transport layer.
3 shows an aza-dibenzothiophene compound and an aza-dibenzofuran compound.
4 shows the reaction in the synthetic route.

In general, an OLED may include one or more organic layers disposed between and electrically connected to the anode and the cathode. When a current is applied, the anode can inject holes into the organic layer (s) and the cathode injects electrons. The injected holes and electrons move to oppositely charged electrodes. When electrons and holes are localized in the same molecule, 'excitons', which are localized electron-hole pairs with excited energy states, are formed. Light is emitted when the exciton is relaxed through the photoluminescence mechanism. In some cases, the exciton can be localized on an excimer or exciplex. Non-radioactive mechanisms such as thermal relaxation may also occur, but are generally considered undesirable.

For example, as disclosed in US Pat. No. 4,769,292, which is incorporated by reference in its entirety, early OLEDs used luminescent molecules that emit from the singlet state ('fluorescent'). Fluorescent luminescence generally occurs in a time frame of less than about 10 nanoseconds.

More recently, OLEDs with light emitting materials that emit from the triplet state ('phosphorescent') have been demonstrated. Baldo ET AL., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," NATURE, Vol. 395, 151-154, 1998; ('Baldo-I') and Baldo ET AL., "Very high-efficiency green. organic light-emitting devices based on electrophosphorescence, "APPL. PHYS. LETT., Vol. 75, no. 3, 4-6 (1999) ("Baldo-II"), which is incorporated by reference in its entirety. Phosphorescence is described in more detail in columns 5-6 of US Pat. No. 7,279,704, which is incorporated by reference.

1 shows an organic light emitting device 100. The figure is not shown to substantially scale. The device 100 includes a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, a light emitting layer 135, a hole blocking layer 140, and an electron transport. The layer 145, the electron injection layer 150, the protective layer 155, and the cathode 160 may be included. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the described layers in sequence. The various layers as well as the properties and functions of the example materials are described in more detail in columns 6-10 of US 7,279,704, which is incorporated by reference.

There may be further examples for each of the layers. For example, soluble and transparent substrate-anode combinations are disclosed in US Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a P doped hole transport layer is m-MTDATA doped with F ₄ TCNQ at a molar ratio of about 50: 1 as disclosed in US Patent Application Publication 2003/0230980, which is incorporated by reference in its entirety. Examples of luminescent and host materials are disclosed in US Pat. No. 6,303,238 to Thompson et al., Which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of about 1: 1, which is disclosed in US Patent Application Publication 2003/0230980, which is incorporated by reference in its entirety. US Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose cathodes comprising a compound cathode having a thin layer of metal, such as Mg: Ag, having an overlapping transparent, electrically conductive sputter-deposited ITO layer. An example of this is disclosed. The theory and use of barrier layers are described in more detail in US Pat. No. 6,097,147 and US Patent Application Publication 2003/0230980, which are incorporated by reference in their entirety. An example of an injection layer is provided in US Patent Application Publication 2004/0174116, which is incorporated by reference in its entirety. A description of the protective layer can be found in US Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, a light emitting layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the described layers in sequence. The most common OLED placement places the cathode on the anode, but since the device 200 places the cathode 215 under the anode 230, the device 200 may be referred to as a 'reverse' OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. 2 provides an example of how some layers may be omitted from the device 100 structure.

The simple layered structures illustrated in FIGS. 1 and 2 are provided as non-limiting examples, and embodiments of the invention may be used in connection with a wide variety of other structures. The particular materials and structures described are substantially exemplary and other materials and structures may be used. Functional OLEDs may be achieved by combining various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described can be used. While many examples provided herein describe various layers comprising a singlet material, it is understood that combinations of materials, such as mixtures of host and dopants, or more generally mixtures, may be used. In addition, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into light emitting layer 220, which may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED can be described as having an 'organic layer' disposed between the cathode and the anode. The organic layer may comprise a single layer or may further comprise multiple layers of different organic materials, for example as described in connection with FIGS. 1 and 2.

Structures and materials not specifically described may also be used, such as, for example, OLEDs (PLEDs) comprised of polymeric materials, such as those disclosed in Friend et al., Incorporated herein by reference in its entirety. As a further example, OLEDs with a single organic layer can be used. OLEDs can be stacked, for example, as described in US Pat. No. 5,707,745 to Forrest et al., Which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate can include an angled reflective surface to improve out-coupling, and is described, for example, in US Pat. No. 6,091,195 (Forrest et al.), Which is incorporated by reference in its entirety. Mesa structures described and / or pit structures described in US Pat. No. 5,834,893 (Bulovic et al.).

Unless otherwise specified, any layer of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjets as described in US Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entirety, and such as those described in Forrest et al., Which are incorporated by reference in their entirety. Organic vapor deposition (OVPD) and deposition by organic vapor jet printing (OVJP) such as described in US Patent Application No. 10 / 233,470, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, low temperature welding and some deposition methods such as those described in US Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety, such as inkjet and OVJP. Other methods can also be used. The material to be deposited can be modified to make it compatible with the particular deposition method. For example, substituents, such as alkyl and aryl groups, which are branched or unbranched and preferably contain three or more carbons, may be used in the small molecule to enhance the ability of the small molecule to be solution processed. Substituents having 20 carbons or more may be used, with 3-20 carbons being the preferred range. Materials having an asymmetrical structure may have better solution processability than those having a symmetrical structure because the asymmetrical material may be less prone to recrystallization. In order to improve the ability of small molecules to be solution processed, dendrimer substituents can be used.

Devices fabricated in accordance with embodiments of the present invention include flat panel displays, computer monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, head up displays, fully transparent displays, flexible displays, laser printers, telephones, It can be incorporated into a wide variety of consumer products, including cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, microdisplays, vehicles, large area walls, theater or stadium screens, or signage. Various control mechanisms can be used to control devices fabricated in accordance with the present invention, including passive and active matrices. Many of the devices are intended for use in a temperature range comfortable to humans, for example 18 ° C. to 30 ° C., and more preferably at room temperature (20 to 25 ° C.).

The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may use these materials and structures. More generally, organic devices such as organic transistors may utilize these materials and structures.

The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, arylalkyl, heterocyclic groups, aryl, aromatic groups and heteroaryl are known in the art and are defined in columns 31-32 of US 7,279,704. Incorporated herein by reference.

A new class of compounds containing aza-dibenzothiophene or aza-dibenzofuran cores is provided (illustrated in FIG. 3). In particular, aza-dibenzothiophene compounds or aza-dibenzofuran compounds further substituted with triphenylene and / or nitrogen containing substituents are provided. Such compounds can be advantageously used in phosphorescent organic light emitting devices. Preferably, such compounds can be used as the host material in the light emitting layer or as the material in the reinforcing layer.

While existing synthesis exists for aza-dibenzothiophene compounds and aza-dibenzofuran compounds, such synthetic routes may have limited feasibility. For example, the substrates of aza-dibenzothiophene and aza-dibenzofuran are known Pschorr rings that include first formation of diazonium salts followed by cyclization in an aqueous medium with or without a catalyst such as Cu, CuCl. Synthesized by Hwa. However, the general yield of the Pschorr cyclization is not constant and may be less than 10%. Thus, it is highly desirable to provide a process for preparing aza-dibenzothiophene compounds and aza-dibenzofuran compounds in improved yields. A new process for preparing aza-dibenzothiophene compounds is provided in the literature (illustrated in FIG. 4). The method described herein differs from conventional synthesis in that it uses at least acetic acid, which is not an aqueous medium, and does not use any metal catalysts. Preferably, the acetic acid is pure acetic acid (or glacial acetic acid). The methods provided herein can provide a yield of at least 50% or a yield of at least 70%.

Dibenzothiophene containing and dibenzofuran containing materials are typically hole transport materials with relatively high triplet energy. Because of the beneficial properties of dibenzothiophene and dibenzofuran, these compounds have been used in the OLED field, and some of these compounds have yielded excellent device performance. Lin et al., Dibenzothiophene-containing Materials in Phosphorescent Light Emitting Diodes, 2008, US Application 12 / 208,907 and Ma et al., Benzo-fused Thiophene / Triphenylene Hybrid Materials, 2008, PCT / US2008 / 072499 ]. Without being bound by theory, it is contemplated that anion implantation and anion stability may play an important role in device stability. In order to obtain high anion stability and a low energy barrier of anion injection into the light emitting layer, compounds with low LUMO levels are preferred. In particular, dibenzothiophene and dibenzofuran containing compounds having low LUMO levels (ie, compounds which are more readily reduced) may be beneficial.

Compounds provided herein contain aza-dibenzothiophene or aza-dibenzofuran cores further substituted with specific chemical groups having desirable properties. In particular, these aza type compounds are substituted with triphenylene groups and / or nitrogen containing groups (eg carbazoles) to maintain high triplet energy and provide improved charge transfer properties. Thus, such aza-dibenzothiophene compounds and aza-dibenzofuran compounds can provide devices with improved stability, improved efficiency and longer lifetime. In addition, it has been found that such aza type compounds can be more easily reduced than their dibenzothiophene or dibenzofuran counterparts to provide devices with lower operating voltages.

Triphenylene is a polyaromatic hydrocarbon with high triplet energy, but high π-conjugation and relatively small energy difference between the first singlet and first triplet levels. This specifies that triphenylene has HOMO and LUMO levels that are relatively easily accessible compared to other aromatic compounds (eg biphenyls) with similar triplet energies. This property of triphenylene gives the OLED host excellent molecular building blocks to stabilize the charge (holes or electrons). One advantage of using triphenylene and its derivatives as hosts is that it can accommodate red, green and even blue phosphorescent dopants to provide high efficiency without energy quenching. Triphenylene hosts can be used to provide high efficiency and stability PHOLEDs. Kwong and Alleyene, Triphenylene Hosts in Phosphorescent Light Emitting Diodes, 2006, 60 pp, U.S. 2006/0280965 Al. Compounds containing aza-dibenzothiophene or aza-dibenzofuran core and triphenylene moiety may be useful as hosts in PHOLEDs. More specifically, the triplet energy of both compound portions is relatively high, thus maintaining a high triplet energy overall. In addition, the combination of these two groups in one compound can also provide improved charge balance to improve device efficiency and lifetime. Non-limiting examples of the triphenylene group which may be the triphenylene portion of such a compound include the following;

Nitrogen containing groups can also be used as substituents for the aza-dibenzothiophene compound and the aza-dibenzofuran compound. Such nitrogen containing groups may include carbazole, oligocarbazole, indolocarbazole and diphenylamine. Carbazole is a nitrogen-containing heteroaromatic with high triplet energy and possesses hole transport and electron transport properties. One advantage of using carbazole-containing compounds (ie carbazole, oligocarbazole and indolocarbazole) as host materials is that they also possess sufficiently large triplet energy and carrier transport properties. For example, the indolocarbazole and 3- (9-carbazolyl) carbazole have a relatively low electrochemical oxidation potential. As such, these compounds are easier to oxidize, and to reverse this oxidation, thereby improving overall host stability. Another advantage is that these carbazole forming blocks can act as donors, while at the same time coupling with the receptors aza-dibenzothiophene or aza-dibenzofuran to form molecules of the donor-receptor type. Such molecules with donor-receptor molecular arrangements are believed to contribute, at least in part, to the low voltage characteristics of the device.

The compounds provided herein can be used as host materials in blue, yellow and red PHOLEDs. In particular, aza-dibenzothiophene or aza-dibenzofuran compounds substituted with triphenylene can be used in blue, green and red devices, as these compounds can accommodate blue, green and red luminescent dopants. have. Preferably such compounds can be used in blue devices. Compounds of the aza type provided herein may also be substituted by both triphenylene and nitrogen containing substituents. Such compounds substituted by both triphenylene and nitrogen containing groups can be used in green and red devices as such compounds can accommodate green and red luminescent dopants. Preferably such compounds can be used in green devices.

The heteroaromatic compounds described herein (ie, aza-dibenzothiophene and aza-dibenzofuran) are more readily reduced than their dibenzothiophene or dibenzofuran counterparts, in particular by 0.2 to 0.5 V. Can be. As a result, such aza type compounds can provide devices with low operating voltages and long lifetimes. Without being bound by theory, it is believed that the more easily reduced compound can provide better anion stability in the device, and easier anion injection from the electron transport layer (ETL) to the light emitting layer (EML). .

The compound has the formula

화학식 (I)

Formula (I)

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are independently selected from the group consisting of carbon and nitrogen atoms, and X ₁ , X ₂ , X ₃ , X ₄ , X _{At least one of 5} , X ₆ , X ₇ and X ₈ is a nitrogen atom. Y is S or O. R ₁ and R ₂ may represent 1, 2, 3 or 4 substitutions. R ₁ and R ₂ are independently selected from the group consisting of hydrogen, alkyl, aryl and halides. At least one of R ₁ and R ₂ is selected from the group consisting of:

R ' ₁ , R' ₂ , R ' ₃ and R' ₄ can represent one, two, three, four or five substitutions and R ' ₁ , R' ₂ , R ' ₃ and R' ₄ is independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. Preferably, R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently hydrogen or methyl.

The compound has the formula

화학식 (I)**

Formula (I)

Wherein X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are independently selected from the group consisting of carbon atoms and nitrogen atoms, and X ₁ , X ₂ , X ₃ , X ₄ At least one of X ₅ , X ₆ , X ₇ and X ₈ is a nitrogen atom. Y is S or O; Wherein R ₁ and R ₂ may represent one, two, three or four substitutions. R ₁ and R ₂ are independently selected from the group consisting of hydrogen, alkyl, aryl and halides, and at least one of R ₁ and R ₂ is selected from the group consisting of:

R ' ₁ , R' ₂ , R ' ₃ and R' ₄ can represent one, two, three, four or five substitutions and R ' ₁ , R' ₂ , R ' ₃ and R' ₄ is independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. Preferably, R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently hydrogen or methyl.

Preferably, m and n are 0, 1, 2, 3 or 4, m + n is at least 2 and m + n is at most 6. Without being bound by theory, it is believed that two or more provide the desired amount of electron transfer portions to provide good electron transfer properties. Moreover, it is believed that greater than 6 can lead to an increase in sublimation temperature, making device fabrication with such compounds unrealistic.

In one embodiment, at least one of R ₁ and R ₂ is selected from the group consisting of:

R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. Preferably, R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently hydrogen or methyl.

Specific examples of such compounds are provided and include compounds selected from the group consisting of:

Specific examples of such compounds are provided and include compounds selected from the group consisting of:

In one embodiment, at least one of R ₁ and R ₂ is selected from the group consisting of:

R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. Preferably, R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently hydrogen or methyl.

Specific examples of such compounds are provided and include compounds selected from the group consisting of:

In one embodiment, at least one of R ₁ and R ₂ is each independently selected from hydrogen and the group consisting of:

R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. Preferably, R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently hydrogen or methyl.

Specific examples of such compounds are provided and include compounds selected from the group consisting of:

In one embodiment, at least one of R ₁ and R ₂ is selected from the group consisting of:

R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. Preferably, R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently hydrogen or methyl.

Specific examples of such compounds include compounds selected from the group consisting of:

In one embodiment, R ₁ and R ₂ are each independently selected from the group consisting of hydrogen and:

R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. Preferably, R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently hydrogen or methyl.

Specific examples of such compounds include compounds selected from the group consisting of:

In one embodiment, R ₁ and R ₂ are each independently selected from the group consisting of hydrogen and:

R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. Preferably, R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently hydrogen or methyl.

Specific examples of such compounds include compounds selected from the group consisting of:

In one embodiment, R ₁ is selected from the group consisting of:

R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. R ₂ is hydrogen. Preferably, R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are each independently hydrogen or methyl.

Specific examples of such compounds include compounds selected from the group consisting of:

A first device is provided that includes an organic light emitting device. The device also includes an anode, a cathode, and an organic layer located between the anode and the cathode. The organic layer includes a compound having formula (I).

화학식 (I)

Formula (I)

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are independently selected from the group consisting of carbon atoms and nitrogen atoms. At least one of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ is a nitrogen atom. Y is S or O. R ₁ and R ₂ may represent 1, 2, 3 or 4 substitutions. R ₁ and R ₂ are independently selected from the group consisting of hydrogen, alkyl, aryl and halides. At least one of R ₁ and R ₂ is selected from the group consisting of:

R ' ₃ and R' ₄ may represent 1, 2, 3, 4 or 5 substitutions. R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl.

In one aspect, the first device is a consumer product.

In addition, an organic light emitting device is provided. The device comprises an anode, a cathode, and an organic layer located between the anode and the cathode, wherein the organic layer comprises a compound having formula (I). Preferably, m and n are 0, 1, 2, 3 or 4; m + n is 2 or more and m + n is 6 or less.

In one embodiment, at least one of R ₁ and R ₂ is selected from the group consisting of:

R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl.

In one embodiment, R ₁ and R ₂ are each independently selected from the group consisting of hydrogen and:

In one embodiment, a device containing a compound selected from the group consisting of Compounds 1-93 is provided.

In particular, a device is provided wherein said compound is a compound selected from the group consisting of Compounds 1-79.

In one embodiment, the organic layer is a light emitting layer, and aza-dibenzothiophene and aza-dibenzofuran having formula (I) are hosts in the organic layer. The organic layer may further include a light emitting dopant. Preferably, the luminescent dopant has the formula:

, 여기서 R₁ 및 R₂는 각각 독립적으로 수소, 알킬 및 아릴로 구성된 군으로부터 선택된다.

, Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, alkyl and aryl.

As discussed above, the aza-dibenzothiophene and aza-dibenzofuran compounds having formula (I) can advantageously be used as host materials in the light emitting layer. However, these compounds can also be used as materials in the reinforcement layer. In particular, the compounds described herein can be used as materials in the barrier layer.

Also provided is a consumer device, wherein the device further comprises an anode, a cathode and an organic layer. The organic layer further comprises an aza-dibenzothiophene or an aza-dibenzofuran compound having the formula (I).

을 갖는 아미노-아릴티오 피리딘 중간체의 아세트산 용액을 ^tBuONO로 처리하여 화학식

을 갖는 아자 착물을 생성하는 것을 포함한다. Y는 S 또는 O이다. X₁ 또는 X₂는 질소이다. R₁ 및 R₂는 1개, 2개, 3개 또는 4개의 치환일 수 있다. R₁은 수소, 알킬, 아릴 및 헤테로아릴로 구성된 군으로부터 선택되고; R₂는 수소, 알킬, 아릴 및 할라이드로 구성된 군으로부터 선택된다. 예를 들어, 피리딘 고리 상의 할라이드 치환을 갖는 중간체 3-아미노-4-아릴티오 피리딘의 아세트산 용액, 또는 상기 피리딘 고리 상에 할라이드 치환을 갖는 중간체 3-아릴티오-4-아미노 피리딘의 아세트산 용액을 ^tBuONO 1∼2 당량에 의해 실온에서 기체가 발생하지 않을 때까지, 일반적으로 1∼3 시간 동안 처리할 수 있다.In addition, a process for preparing an aza-dibenzothiophene compound or an aza-dibenzofuran compound is provided (illustrated at the top of FIG. 4). The method is formula

The acetic acid solution of the amino-arylthio pyridine intermediate with ^t BuONO

Generating an aza complex having: Y is S or O. X ₁ or X ₂ is nitrogen. R ₁ and R ₂ may be one, two, three or four substitutions. R ₁ is selected from the group consisting of hydrogen, alkyl, aryl and heteroaryl; R ₂ is selected from the group consisting of hydrogen, alkyl, aryl and halides. For example, an acetic acid solution of intermediate 3-amino-4-arylthio pyridine with a halide substitution on a pyridine ring or an acetic acid solution of intermediate 3-arylthio-4-amino pyridine with a halide substitution on the pyridine ring is ^t By 1 to 2 equivalents of BuONO, it can be treated for 1 to 3 hours until no gas is generated at room temperature.

의 수율은 50% 이상일 수 있다.In particular, examples of such methods include intermediates and aza complexes, where Y is S (ie, dibenzothiophene intermediates and aza-dibenzothiophene complexes). Alternatively, the method preferably comprises an intermediate and an aza complex, wherein Y is O (ie, a dibenzofuran intermediate and an aza-dibenzofuran complex). The methods provided herein can yield at least 50% or at least 70% of the aza complex. Specifically,

The yield of may be at least 50%.

Examples of methods for preparing aza-dibenzothiophene or aza-dibenzofuran compounds include intermediates in which one of X ₁ and X ₂ is carbon and the other is nitrogen. In an embodiment of the method, X ₁ is nitrogen and X ₂ is carbon. In another specific example, X ₁ is carbon and X ₂ is nitrogen.

Examples of methods for the preparation of aza-dibenzothiophene or aza-dibenzofuran compounds include compounds in which R ₂ comprises at least one halide. In an embodiment of the method, R ₂ comprises only halide substitutions. Moreover, R ₁ is preferably halide. Halide substituents may include, but are not limited to bromide, chloride, fluoride and iodide.

The method can also be used to prepare aza-dibenzothiophene or aza-dibenzofuran compounds in which R ₂ is not a halide (ie there is no further substituent on the pyridine ring). For these aza compounds without halide substituents on the pyridine ring, the amino-arylthio pyridine intermediate is treated with H ₂ SO ₄ before treatment with ^t BuONO (illustrated in FIG. 4 bottom). For example, the acetic acid solution of the intermediate 3-amino-4-arylthio pyridine or the acetic acid solution of the intermediate 3-arylthio-4-amino pyridine is treated with 5 equivalents of H ₂ SO ₄ , then ₁ to 2 equivalents ^T BuONO can generally be treated for about 1 to 5 hours until no gas is generated.

Materials described herein as useful for certain layers of organic light emitting devices can be used in combination with various other materials present in the devices. For example, the luminescent dopants disclosed herein can be used with various hosts, transfer layers, barrier layers, injection layers, electrodes, and other possible layers. The following description or materials mentioned are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of ordinary skill in the art can readily advise the literature to identify other materials that may be useful in combination.

In addition to and / or in combination with the materials disclosed herein, many hole injection materials, hole transport materials, host materials, dopant materials, exciton / hole blocking layer materials, electron transport and electron injection materials can be used in the OLED. Non-limiting examples of materials that can be used in combination with materials described herein in OLEDs are listed in Table 1 below. Table 1 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose such materials.

Table 1

Example

Compound example

Example 1 Synthesis of Compound 1

화합물 1

Compound 1

Step 1 . 2-chloro-3-iodo-4-aminopyridine (10 g, 39 mmol), 4-bromothiophenol (7.0 g, 34 mmol), CuI (0.4 g, 2.0 mmol), ethylene in a 500 mL round flask Glycol (4.9 g, 78 mmol), potassium carbonate (10.8 g, 74 mmol) and 200 mL of isopropanol were added. The reaction was heated to reflux and stirred for 24 h under a nitrogen atmosphere. After cooling, the mixture was purified by silica gel column. The yield of 2-chloro-3- (4-bromophenylthio) -4-aminopyridine was 7.4 g.

Step 2 . To a 500 mL round flask was added 2-chloro-3- (4-bromophenylthio) -4-aminopyridine (7.0 g, 22 mmol), and 400 mL of AcOH. To this clear solution, Bu'ONO (2.3 g, 22 mmol) was added dropwise. After stirring for 1 hour at room temperature, another 10 mmol of Bu ^t ONO were added. The mixture was kept stirring for an additional 2 hours. The reaction was quenched with water and the product was purified by silica gel column. The yield of 1-chloro-6-bromo- [1] benzothieno [2,3-c] pyridine was 6.5 g.

Step 3 . In a 500 mL round flask, 1-chloro-6-bromo- [1] benzothieno [2,3-c] pyridine (3.6 g, 12 mmol), carbazole (6.0 g, 36 mmol), Pd ₂ (dba ) ₃ (1.1 g, 1.2 mmol), 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (S-Phos, 2.0 g, 4.8 mmol), sodium t-butoxide (6.9 g, 72 mmol) and 250 mL of xylene were added. The reaction was heated to reflux and stirred for 24 h under a nitrogen atmosphere. After cooling, the mixture was purified by silica gel column. The yield was 4.0 g. The product was further purified by reduced pressure sublimation. ¹ H NMR results confirmed the desired compound.

Example 2. Synthesis of Compound 2

화합물 2

Compound 2

Step 1 . In a 500 mL round flask, 2-chloro-4-amino-5-iodo-pyridine (11.5 g, 45 mmol), 4-bromothiophenol (8.1 g, 42.8 mmol), CuI (0.4 g, 2.3 mmol), Ethylene glycol (5.6 g, 90.4 mmol), potassium carbonate (12.4 g, 90.4 mmol) and 200 mL of isopropanol were added. The reaction was heated to reflux and stirred for 24 h under a nitrogen atmosphere. After cooling, the mixture was purified by silica gel column. The yield of 2-chloro-5- (4-bromophenylthio) -4-aminopyridine was 9.2 g.

Step 2. To a 500 mL round flask was added 2-chloro-5- (4-bromophenylthio) -4-aminopyridine (11 g, 35 mmol) and 600 mL of AcOH. To this clear solution, Bu ^t ONO (3.6 g, 35 mmol) was added dropwise. After stirring for 1 hour at room temperature, another 15 mmol of Bu ^t ONO were added. The mixture was kept stirring for an additional 2 hours. The reaction was quenched with water and the product was purified by silica gel column. The yield of 3-chloro-6-bromo- [1] benzothieno [2,3-c] pyridine was 10 g.

Step 3 . In a 500 mL round flask, 3-chloro-6-bromo- [1] benzothieno [2,3-c] pyridine (3.0 g, 10 mmol), carbazole (4.2 g, 25 mmol), Pd (OAc) ₂ (0.1 g, 0.5 mmol), P (Bu ') ₃ (1 M in toluene, 1.5 mL, 1.5 mmol), sodium t-butoxide (6.3 g, 66 mmol) and 250 mL of xylene were added. The reaction was heated to reflux and stirred for 24 h under a nitrogen atmosphere. After cooling, the mixture was purified by silica gel column. The yield was 4.2 g. The product was further purified by reduced pressure sublimation. ¹ H NMR results confirmed the desired compound.

Example 3. Synthesis of Compound 3

Step 1 . In a 500 mL round flask, 2,6-dichloro-3-iodo-4-aminopyridine (7.0 g, 28.8 mmol), thiophenol (3.2 g, 34.8 mmol), CuI (0.2 g, 1.2 mmol), ethylene glycol ( 3.0 g, 57.6 mmol), potassium carbonate (6.6 g, 57.6 mmol) and 200 mL of isopropanol were added. The reaction was heated to reflux and stirred for 24 h under a nitrogen atmosphere. After cooling, the mixture was purified by silica gel column. The yield of 2,6-dichloro-3-phenylthio-4-aminopyridine was 4.0 g.

Step 2 . To a 500 mL round flask was added 2,6-dichloro-3-phenylthio-4-aminopyridine (4.0 g, 14.7 mmol) and 200 mL of AcOH. To this clear solution, Bu ^t ONO (1.5 g, 15 mmol) was added dropwise. After stirring for 1 hour at room temperature, another 8 mmol of Bu ^t ONO was added. The mixture was kept stirring for an additional 2 hours. The reaction was quenched with water and the product was purified by silica gel column. The yield of 1,3-dichloro- [1] benzothieno [2,3-c] pyridine was 3.2 g.

Step 3 . In a 500 mL round flask, 1,3-dichloro- [1] benzothieno [2,3-c] pyridine (2.5 g, 10 mmol), carbazole (4.2 g, 25 mmol), Pd ₂ (dba) ₃ ( 0.9 g, 1.0 mmol), 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (S-Phos, 1.6 g, 4.0 mmol), sodium t-butoxide (4.8 g, 50 mmol) and 200 mL of xylene was added. The reaction was heated to reflux and stirred for 24 h under a nitrogen atmosphere. After cooling, the mixture was purified by silica gel column. The yield was 4.2 g. The product was further purified by reduced pressure sublimation. ¹ H NMR results confirmed the desired compound.

Example 4. Synthesis of Compound 4

화합물 4

Compound 4

Step 1 . In a 500 mL round flask, 1-chloro-6-bromo- [1] benzothieno [2,3-c] pyridine (5.0 g, 16.7 mmol), carbazole (2.8 g, 16.7 mmol), Pd (OAc) ₂ (0.1 g, 0.4 mmol), PBu ^t ₃ (1.0 M solution in toluene, 1.2 mL, 1.2 mmol), sodium t-butoxide (4.8 g, 50.1 mmol) and 400 mL of xylene were added. The reaction was heated to reflux and stirred for 24 h under a nitrogen atmosphere. After cooling, the mixture was purified by silica gel column. The yield of 1-chloro-6- (9-carbazole)-[1] benzothieno [2,3-c] pyridine was 1.9 g.

Step 2 . In a 500 mL round flask, 1-chloro-6- (9-carbazole)-[1] benzothieno [2,3-c] pyridine (1.3 g, 3.4 mmol), diphenylamine (0.7 g, 4.0 mmol) , Pd ₂ (dba) ₃ (0.09 g, 0.1 mmol), 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (0.2 g, 0.4 mmol), sodium t-butoxide (0.8 g, 8.0 mmol) and 100 mL of toluene were added. The reaction was heated to reflux and stirred for 24 h under a nitrogen atmosphere. After cooling, the mixture was purified by silica gel column. The yield of compound 4 was 1.1 g.

Example 5. Synthesis of Compound 21

화합물 21

Compound 21

Step 1 . A solution of 2-amino-5-chloropyridine (10.0 g, 77.8 mmol), potassium acetate (7.63 g, 77.8 mmol) in 100 mL acetic acid was heated to 85 ° C. and ClI (12.6 g, 77.8 in 50 mL acetic acid). mmol) was added dropwise. The reaction mixture was maintained at this temperature for 2 hours, then diluted with 1 L of water, neutralized to pH 7 with NaOH IN and extracted with ethyl acetate (4 x 75 mL). The organic fractions were combined, washed with NaHCO ₃ , filtered through celite and evaporated. The residue was treated by column chromatography on silica (eluent-hexane / ethyl acetate 1/1) to yield 5-chloro-3-iodopyridin-2-amine (11.9 g, 60%) as a yellow solid.

Step 2 . 5-chloro-2-methoxyphenylboronic acid (5.0 g, 26.8 mmol), 5-chloro-3-iodopyridin-2-amine (6.83 g, 26.8 mmol), sodium carbonate (8.53 g, in 50 mL of water) 80.5 mmol), Pd (PPh ₃ ) ₄ (621 mg, 2 mol%) and 100 mL of toluene were refluxed under N ₂ overnight. The reaction mixture was cooled to room temperature, the organic layer was separated and concentrated in vacuo. The residue was treated by column chromatography on silica gel with a hexane / ethyl acetate gradient as eluent to give 3.3 g (46% yield) of 5-chloro-3- (5-chloro-2-methoxyphenyl) pyridin-2-amine. ).

Step 3 . A solution of 5-chloro-3- (5-chloro-2-methoxyphenyl) pyridin-2-amine (5.2 g, 19.3 mmol) in 50 mL glacial acetic acid and 20 mL THF was cooled to -10 ° C, tert Butyl nitrite (4.6 mL) was added dropwise. The reaction mixture was stirred overnight at 0 ° C., cooled to room temperature and diluted with 100 mL of water. The solid material was filtered and dried to yield 2.9 g of pure 3,6-dichlorobenzofuro [2,3-b] pyridine.

Step 4 . 3,6-dichlorobenzofuro [2,3-b] pyridine (2.86 g, 12.01 mmol), carbazole (5.02 g, 30.003 mmol), sodium tert-butoxide (4.62 g, 48.05 mmol) in 150 mL of dry xylene ), A mixture of 2-dicyclohexyl-phosphino-2 ', 6'-dimethoxybiphenyl (S-Phos, 430 mg), Pd ₂ (dba) ₃ (910 mg) was refluxed under N ₂ for 48 hours. I was. The reaction mixture was then cooled to room temperature, diluted with 100 mL H ₂ O and extracted with ethyl acetate (4 x 50 mL). The organic fractions were combined, dried over Na ₂ SO ₄ anhydride, filtered and evaporated. The residual material was purified by column chromatography on silica gel (eluent-gradient mixture hexane-dichloromethane) and then crystallized from the hexane / dichloromethane mixture to yield a white small needle target material. Further purification by sublimation (288 ° C. at 10 ⁻⁵ mmHg) yielded 1.86 g of pure target compound.

Example 6. Synthesis of Compound 39

화합물 39

Compound 39

Step 1 . 3-Chloro-6-bromo- [1] benzothieno [2,3-c] pyridine (1.7 g, 5.8 mmol), triphenylene-2-ylboronic acid (1.6 g, 5.8 mmol), triphosphate A mixture of potassium (3.7 g, 17 mmol), 200 mL of toluene and 10 mL of water was prepared and bubbled with nitrogen for 20 minutes. Tris (dibenzylideneacetone) dipalladium (53 mg, 0.060 mmol) and 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (96 mg, 0.23 mmol) were then added. The mixture was bubbled with nitrogen for an additional 20 minutes. After refluxing under nitrogen overnight, the reaction mixture was cooled to room temperature, filtered through a plug of silica and washed with dichloromethane. The first few parts were discarded because they only contained impurities. The combined filtrates were concentrated to yield crude product, which was recrystallized from hot dichloromethane and hexanes to give a yellow solid 3-chloro-6- (2-triphenylenyl)-[1] benzothieno [2, 3-c] pyridine 1.8 g (4.0 mmol, 70% yield) was calculated.

Step 2 . 3-chloro-6- (2-triphenylenyl)-[1] benzothieno [2,3-c] pyridine (1.6 g, 3.6 mmol), carbazole (0.72 g, 4.3 mmol), Pd (OAc) A mixture of ₂ (20 mg, 0.090 mmol), sodium t-butoxide (1.0 g, 11 mmol) and 300 mL of xylene was prepared and bubbled with nitrogen for 15 minutes. PBu ^t ₃ (1.0 M solution in toluene, 0.27 mL, 0.27 mmol) was then added and the mixture was bubbled with nitrogen for an additional 15 minutes. After refluxing overnight, the reaction mixture was cooled to room temperature and filtered through a silica gel plug, which was then washed with dichloromethane. The xylene was discarded. The combined dichloromethane filtrate was concentrated and the crude product was stirred overnight in a 100 mL mixture of 20% dichloromethane in hexanes. The residue was collected by filtration to yield 1.7 g (2.9 mmol, 80% yield) of a pale yellow solid.

Example 7. Synthesis of Compound 59

화합물 59

Compound 59

Step 1 . 1-chloro-6- (9-carbazole)-[1] benzothieno [2,3-c] pyridine (1.0 g, 1.6 mmol), triphenylene-2-ylboronic acid (0.85 g, 3.1 mmol) A mixture of, potassium triphosphate (1.7 g, 7.8 mmol), 100 mL of toluene and 5 mL of water was prepared and bubbled with nitrogen for 20 minutes. Then tris (dibenzylideneacetone) dipalladium (24 mg, 0.030 mmol) and 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (43 mg, 0.10 mmol) were added. The mixture was bubbled with nitrogen for an additional 20 minutes. After refluxing under nitrogen overnight, the reaction was cooled to room temperature and concentrated. The solid obtained was redissolved in 800 mL of reflux toluene and filtered through a thin plug of celite. The collected filtrate was filtered to about 100 mL and then refluxed under nitrogen for 1 hour. After slowly cooling to room temperature, the precipitate was collected by filtration. The residue was stirred in 100 mL hot mixture of 20% dichloromethane in methanol, which was cooled to room temperature and then stirred overnight. The residue was collected by filtration and dried under vacuum to yield 1.2 g (2.1 mmol, 81% yield) of a white solid.

Example 8. Synthesis of Compound 66

화합물 66

Compound 66

Step 1 . 2-chloro-3-iodo-4-aminopyridine (5.0 g, 19.6 mmol), thiophenol (2.16 g, 19.6 mmol), CuI (0.187 g, 0.98 mmol), ethylene glycol (2.5 g) in a 250 mL round flask , 39 mmol), potassium carbonate (5.4 g, 39 mmol) and 150 mL of isopropanol were added. The reaction was heated to reflux and stirred for 24 h under a nitrogen atmosphere. After cooling, the mixture was purified by silica gel column. The yield of 2-chloro-3-phenylthio-4-aminopyridine was 4.2 g (91%).

Step 2 . To a 250 mL round flask was added 2-chloro-3-phenylthio-4-aminopyridine (2.7 g, 11.4 mmol) and 60 mL of glacial acetic acid. To this clear solution, Bu ^t ONO (1.36 g, 11.45 mmol) was added dropwise. After stirring for 1 h at rt, additional (1.36 g 11.45) mmol of Bu ^t ONO was added. The mixture was kept stirring for 18 hours at room temperature. The reaction was quenched with water and the product was purified by silica gel column. The yield of 1-chloro-benzothieno [2,3-c] pyridine was 2.2 g (88%).

Step 3. 1-chloro-benzothieno [2,3-c] pyridine (1.5 g, 6.8 mmol), 3- (triphenylen-2-yl) phenylboronic acid (2.5 g) synthesized according to US provisional application 60 / 963,944 , 7.2 mmol), tribasic potassium phosphate (4.4 g, 20.4 mmol), 100 mL of toluene and 10 mL of water were prepared and bubbled with nitrogen for 15 minutes. Then tris (dibenzylideneacetone) dipalladium (63 mg, 0.068 mmol) and 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (116 mg, 0.28 mmol) were added. The mixture was bubbled with nitrogen for an additional 20 minutes. After refluxing under nitrogen overnight, the reaction mixture was cooled to room temperature. The product was purified by silica gel chromatography column. 2.7 g (81%) of Compound 66 were obtained.

Example 9. Synthesis of Compound 70

화합물 70

Compound 70

Step 1 . 1-chloro-benzothieno [2,3-c] pyridine (1.0 g, 4.5 mmol), 2-triphenylene-boronic acid (1.25 g, 4.5 mmol) synthesized according to US provisional application 60 / 963,944, first A mixture of potassium triphosphate (3.0 g, 18.0 mmol), 100 mL of toluene and 10 mL of water was prepared and bubbled with nitrogen for 15 minutes. Then tris (dibenzylideneacetone) dipalladium (42 mg, 0.045 mmol) and 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (77 mg, 0.18 mmol) were added. The mixture was bubbled with nitrogen for an additional 20 minutes. After refluxing under nitrogen overnight, the reaction mixture was cooled to room temperature. The product was purified by silica gel chromatography column. ˜1.5 g (84%) of compound 70 was obtained.

Example 10. Synthesis of Compound 71

화합물 71

Compound 71

Step 1 . A solution of 2-amino-5-chloropyridine (10.0 g, 77.8 mmol) potassium acetate (7.63 g, 77.8 mmol) in 100 mL acetic acid was heated to 85 ° C. and ClI (12.6 g, 77.8 mmol) in 50 mL acetic acid. ) Was added dropwise. The reaction mixture was maintained at this temperature for 2 hours, diluted with 1 L of water, neutralized to pH 7 with NaOH IN solution and extracted with ethyl acetate (4 x 75 mL). The organic fractions were combined, washed with NaHCO ₃ , filtered through celite and evaporated. The residue was treated by column chromatography on silica gel (eluent-hexanes / ethyl acetate 1/1) to yield a yellow solid 5-chloro-3-iodopyridin-2-amine (11.9 g, 60%).

Step 2. 2- (methylthio) phenylboronic acid (5.0 g, 29.8 mmol), 5-chloro-3-iodopyridin-2-amine (7.56 g, 29.8 mmol), sodium carbonate (9.0 g, 50 mL water), Pd A mixture of (PPh ₃ ) ₄ (621 mg) and 100 mL of toluene was refluxed under N ₂ overnight. The reaction mixture was cooled to rt, the organic layer was separated and concentrated in vacuo. The residue was treated by column chromatography on silica gel with a hexane / ethyl acetate gradient mixture as eluent to yield 3.5 g of 5-chloro-3- (2- (methylthio) phenyl) pyridin-2-amine. It was.

Step 3 . A solution of 5-chloro-3- (2- (methylthio) phenyl) pyridin-2-amine (5.2 g, 19.3 mmol) in 50 mL glacial acetic acid and 20 mL THF was cooled to -10 ° C, tert-butyl Nitrite (4.6 mL) was added dropwise. The reaction mixture was stirred at 0 ° C. overnight, warmed to rt and diluted with 100 mL of water. The solid material was filtered and dried to yield 2.5 g of pure 3-chlorobenzothieno [2,3-b] pyridine.

Step 4. 3-Chloro- [1] benzothieno [2,3-b] pyridine (1.3 g, 5.9 mmol), 4,4,5,5-tetramethyl-2- (3- (triphenylene- Prepare a mixture of 2-yl) phenyl) -1,3,2-dioxaborolane (3.1 g, 7.1 mmol), potassium triphosphate (3.8 g, 18 mmol), 100 mL of toluene and 10 mL water, Bubble with nitrogen for 15 minutes. Then tris (dibenzylideneacetone) dipalladium (54 mg, 0.060 mmol) and 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (97 mg, 0.24 mmol) were added. The mixture was bubbled with nitrogen for an additional 20 minutes. After refluxing under nitrogen overnight, the reaction mixture was cooled to room temperature and filtered to collect the precipitate. The residue was washed with methanol and then redissolved in hot toluene. The solution was filtered through a magnesium sulfate plug, which was washed with dichloromethane. The combined filtrates were concentrated to yield 700 mg (1.4 mmol, 24% yield) of a white solid.

Example 11. Synthesis of Compound 79

화합물 79

Compound 79

Step 1. 2-chloro-5-iodo-4-aminopyridine (5.0 g, 19.6 mmol), thiophenol (2.16 g, 19.6 mmol), CuI (0.187 g, 0.98 mmol), ethylene glycol (2.5 g) in a 250 mL round flask , 39 mmol), potassium carbonate (5.4 g, 39 mmol) and 150 mL of isopropanol were added. The reaction was heated to reflux and stirred for 24 h under a nitrogen atmosphere. After cooling, the mixture was purified by silica gel column. The yield of 2-chloro-3-phenylthio-4-aminopyridine was 4.5 g.

Step 2 . To a 250 mL round flask was added 2-chloro-3-phenylthio-4-aminopyridine (3.7 g, 16.8 mmol) and 60 mL of glacial acetic acid. To this clear solution, Bu ^t ONO (1.8 g, 16.8 mmol) was added dropwise. After stirring for 1 hour at room temperature, additional (1.8 g 16.8) mmol of Bu ^t ONO was added. The mixture was kept stirring for 18 hours at room temperature. The reaction was quenched with water and the product was purified by silica gel column. The yield of 3-chloro-benzothieno [2,3-c] pyridine was 1.2 g (33%).

Step 3 . 3-chloro-benzothieno [2,3-c] pyridine (1.0 g, 4.5 mmol), 3- (triphenylen-2-yl) phenylboronic acid (2.1 g) synthesized according to US provisional application 60 / 963,944 , 4.8 mmol), tribasic potassium phosphate (2.9 g, 13.5 mmol), 100 mL of toluene and 10 mL of water were prepared and bubbled with nitrogen for 15 minutes. Then tris (dibenzylideneacetone) dipalladium (63 mg, 0.068 mmol) and 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (116 mg, 0.28 mmol) were added. The mixture was bubbled with nitrogen for an additional 20 minutes. After refluxing under nitrogen overnight, the reaction mixture was cooled to room temperature. The product was purified by silica gel chromatography column. ˜1.2 g (55%) of compound 79 was obtained.

Example 12. Synthesis of Compound 80

화합물 80

Compound 80

Step 1 . Carbazole (7.3 g, 43.7 mmol), 3-bromoiodobenzene (25 g, 87.3 mmol) and sodium t-butoxide (8.4 g, 87.3 mmol) were suspended in 150 ml of dry xylene under a nitrogen atmosphere. Tris (dibenzylideneacetone) dipalladium (200 mg) and 1,1'-bis (diphenylphosphino) ferrocene (400 mg) are added in one aliquot, the reaction is heated to reflux, and under nitrogen atmosphere 24 Stir for hours. After cooling, the xylene was evaporated and the residue was treated by column chromatography on silica gel to yield 3-bromophenyl carbazole (9.5 g, yellow solidified oil).

Step 2 . 3-bromophenyl carbazole (9.5 g, 29.5 mmol), bis (pinacolato) diboron (11.2 g, 44.2 mmol), potassium acetate (8.7 g), tris (dibenzylideneacetone) dipalladium (200 mg ) And 1,1'-bis (diphenylphosphino) ferrocene (400 mg) were suspended in 200 mL of dioxane and heated to reflux overnight under nitrogen atmosphere. After cooling and evaporation, the residue was treated by column chromatography on silica gel to give 9- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl ) Phenyl) -9H-carbazole b (6.0 g, colorless crystals) was calculated.

Step 3 . 1,3-dibromobenzene (16 g, 64.9 mmol), 9- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -9H-carbazole b (6.0 g, 11.6 mmol), potassium acetate (6.6 g saturated solution in water) and tetrakis (triphenylphosphine) palladium (0) (380 mg) under nitrogen atmosphere 150 mL of toluene Heated to reflux overnight at. After cooling, steaming and column chromatography, 9- (3'-bromo- [1,1'-biphenyl] -3-yl) -9H-carbazole (5.8 g) was obtained.

Step 4 . Under the same conditions as in step 2, bis (pinacolato) diboron in dioxane and 9- (3 catalyzed with tris (dibenzylideneacetone) dipalladium and 1,1'-bis (diphenylphosphino) ferrocene '-Bromo- [1,1'-biphenyl] -3-yl) -9H-carbazole is reacted with potassium acetate as a base to give 9- (3'-(4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl] -3-yl) -9H-carbazole was yielded and purified by column chromatography on silica gel. .

Step 5 . 1-chlorobenzo [4,5] thieno [2.3-c] pyridine (described as compound 66, step 2) and 9- (3 ′-(4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl)-[1,1'-biphenyl] -3-yl) -9H-carbazole was dissolved in toluene (150 mL). In one aliquot of the catalyst (tris (dibenzylideneacetone) dipalladium, 400 mg and 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl, 200 mg) and base (potassium triphosphate) The reaction was added and heated to reflux overnight under a nitrogen atmosphere. The product was purified by silica gel column to yield Compound 80.

Device example

All example devices were prepared by high vacuum (<10 ⁻⁷ Torr) thermal evaporation. The anode electrode is 800 kPa of indium tin oxide (ITO). The cathode consists of LiF 10 kPa and Al 1000 kPa. All devices were charged in a nitrogen glove box (H ₂ O and O ₂ <1 ppm) immediately after the production of a glass lid sealed with an epoxy resin and encapsulated by, moisture getters (moisture getter) in the package.

Certain devices are provided wherein P1 is a luminescent dopant and the compound, compound 1, compound 2 or compound 3 of the present invention is a host. The organic stacks of the device examples 1 to 3 were sequentially from the surface of the ITO, P1 100 GPa as the hole injection layer (HIL), and 4,4'-bis [N- (l-naphthyl) -N as the hole transport layer (HTL). -Phenylamino] biphenyl (α-NPD) 3O ', Compound 300' of the present invention doped with P1, Ir phosphorescent compound 15% as light emitting layer (EML), Compound 100 'of the present invention as ETL2 and Alq ₃ as ETL1 (Tris-8-hydroxyquinoline aluminum) 400 kPa.

Comparative Example 1 was prepared similar to the device example above except that EML included CBP as the host doped with P1 10% and P2 was used as the barrier layer material.

As used herein, the following compound has the structure:

Certain materials are provided for use in OLEDs, which can lead to devices having particularly good properties. The material may be used as a host of the light emitting layer or as a material in the reinforcing layer. Table 2 shows the light emitting layer material and the blocking layer material of the device examples 1 to 3. The device was tested and the measured results are given in Table 3. Cmpd stands for compound. Devices having light emitting and blocking layers using compounds 1 to 3 exhibited high device efficiency, long life and reduced operating voltage.

TABLE 2

TABLE 3

It can be seen from device examples 1 to 3 that the compounds of the invention as hosts in green phosphorescent OLEDs provide high efficiency (ie LE> 60 cd / A at 1000 cd / m ² ), which is aza as chromophore. Indicates that dibenzothiophene possesses triplets high enough for efficient green field phosphorescence. Also of note is the high stability of the devices comprising compounds 1 and 2 as hosts. The lifetime T _80% (defined as the time required for the initial luminance L ₀ to decrease to 80% of its value at a constant current density of 40 mA / cm ² at room temperature) is 113 hours and 85 for compounds 1 and 2, respectively. It is time and L <_0> is higher than the comparative example 1. This means a 1.5x improvement in device stability. Thus, the compounds of the present invention can function well as reinforcing layers.

Another notable feature is the compound 1 and 2 both have, of 5.2 V at lOOO cd / m low device voltage compared to the CBP having a 5.8 V at ^{2, 1000 cd / m 2 5} V and 1000 cd / m ² at Is the point.

The data suggest that aza-dibenzothiophene can be a good host and enhancement layer in phosphorescent OLEDs, providing high efficiency, low voltage and several times better device stability improvements than commonly used host CBP.

It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention. Thus, the invention as claimed may include variations from the specific and preferred embodiments described herein, as will be apparent to one of ordinary skill in the art. It is to be understood that various theories as to the principles of operation of the invention are not limited.

Claims (15)

Compounds having the general formula (I)
Formula (I)

In the above formula,
m and n are 0, 1, 2, 3 or 4;
m + n is at least 1;
X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are independently selected from the group consisting of carbon atoms and nitrogen atoms;
_{Two of} X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are nitrogen atoms;
Y is S or O;
R ₁ and R ₂ are independently selected from the group consisting of hydrogen, alkyl, aryl and halides;
At least one of R ₁ and R ₂

Is selected from the group consisting of; here
R ' ₁ , R' ₂ , R ' ₃ and R' ₄ represent one, two, three or four substituted or unsubstituted,
R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. The method of claim 1, wherein at least one of R ₁ and R ₂ is

Phosphorus compounds. The compound of claim 2, wherein m and n are 0, 1, 2, 3 or 4, m + n is at least 2 and m + n is at most 6. 6. A first device comprising an organic light emitting device,
Anode;
Cathode; And
An organic layer located between the anode and the cathode, the organic layer further comprising a compound having formula (I)
The first device further comprising:
Formula (I)

In the above formula,
m and n are 0, 1, 2, 3 or 4;
m + n is at least 1;
X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are independently selected from the group consisting of carbon atoms and nitrogen atoms;
_{Two of} X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are nitrogen atoms;
Y is S or O;
R ₁ and R ₂ are independently selected from the group consisting of hydrogen, alkyl, aryl and halides;
At least one of R ₁ and R ₂

Is selected from the group consisting of; here
R ' ₁ , R' ₂ , R ' ₃ and R' ₄ represent one, two, three or four substituted or unsubstituted,
R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. The first device of claim 4, wherein the first device is a consumer product. The method of claim 4, wherein at least one of R ₁ and R ₂ is

The first device. The method of claim 4, wherein the organic layer is a light emitting layer,
Formula (I)

A first device wherein the compound having a host is a host. The first device of claim 4, wherein the organic layer further comprises a luminescent dopant, wherein the luminescent dopant has the formula:

In the above formula, R ₁ and R ₂ of the luminescent dopant are each independently selected from the group consisting of hydrogen, alkyl and aryl. Compounds having the general formula (I)
Formula (I)

In the above formula,
m and n are 0, 1, 2, 3 or 4;
m + n is at least 1;
X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are independently selected from the group consisting of carbon atoms and nitrogen atoms;
_{X 1, X 2, X 3} , X 4, X 5, X 6, X 7 and X ₈ 2 of which are nitrogen atoms and;
Y is S or O;
R ₁ and R ₂ are independently selected from the group consisting of hydrogen, alkyl, aryl and halides;
At least one of R ₁ and R ₂

Is selected from the group consisting of; here
R ' ₁ , R' ₂ , R ' ₃ and R' ₄ represent one, two, three or four substituted or unsubstituted,
R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. Compounds having the general formula (I)
Formula (I)

In the above formula,
m and n are 0, 1, 2, 3 or 4;
m + n is at least 1;
X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are independently selected from the group consisting of carbon atoms and nitrogen atoms;
_{Two of} X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are nitrogen atoms;
Y is S or O;
R ₁ and R ₂ are independently hydrogen, alkyl, aryl, halide,

Is selected from the group consisting of;
At least one of R ₁ and R ₂ present in the compound

Is selected from the group consisting of; here
R ' ₁ and R' ₂ represent 1, 2, 3, or 4 substituted or unsubstituted,
R ' ₁ and R' ₂ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. 11. The compound of claim 10, wherein m + n is at least 2 and m + n is at most 6. A first device comprising a first organic light emitting device,
Anode;
Cathode; And
An organic layer located between the anode and the cathode, the organic layer further comprising a compound having formula (I)
The first device further comprising:
Formula (I)

In the above formula,
m and n are 0, 1, 2, 3 or 4;
m + n is at least 1;
X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are independently selected from the group consisting of carbon atoms and nitrogen atoms;
_{Two of} X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are nitrogen atoms;
Y is S or O;
R ₁ and R ₂ are independently hydrogen, alkyl, aryl, halide,

Is selected from the group consisting of;
At least one of R ₁ and R ₂ present in the compound

Is selected from the group consisting of; here
R ' ₁ and R' ₂ represent 1, 2, 3, or 4 substituted or unsubstituted,
R ' ₁ and R' ₂ are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl, aryl and heteroaryl. The first device of claim 12, wherein the first device is a consumer product. The method of claim 12, wherein the organic layer is a light emitting layer,
Formula (I)

A first device wherein the compound having a host is a host. The first device of claim 12, wherein the organic layer further comprises a luminescent dopant, wherein the luminescent dopant has the formula:

In the above formula, R ₁ and R ₂ of the luminescent dopant are each independently selected from the group consisting of hydrogen, alkyl and aryl.

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